Energy Bands in Solids:

➢ According to Quantum Mechanical Laws, the energies of electrons in a

free atom can not have arbitrary values but only some definite
(quantized) values.
➢ However, if an atom belongs to a crystal, then the energy levels are
modified.
➢ This modification is not appreciable in the case of energy levels of
electrons in the inner shells (completely filled).
➢ But in the outermost shells, modification is appreciable because the
electrons are shared by many neighbouring atoms.
➢ Due to influence of high electric field between the core of the atoms and
the shared electrons, energy levels are split-up or spread out forming
energy bands.

Consider a single crystal of silicon having N atoms. Each atom can be

associated with a lattice site.
Electronic configuration of Si is 1s2, 2s2, 2p6,3s2, 3p2. (Atomic No. is 14)
Formation of Energy Bands in Solids:

Energy

Conduction Band
• • 3p2
Forbidden Energy Gap • • 3s2
Valence Band

•••••• 2p6 Ion

• • 2s2 core
state
• • 1s2

O a b c d Inter atomic spacing (r)

(i) r = Od (>> Oa):
Each of N atoms has its own energy levels. The energy levels are identical,
sharp, discrete and distinct.
The outer two sub-shells (3s and 3p of M shell or n = 3 shell) of silicon atom
contain two s electrons and two p electrons. So, there are 2N electrons
completely filling 2N possible s levels, all of which are at the same energy.
Of the 6N possible p levels, only 2N are filled and all the filled p levels have
the same energy.
(ii) Oc < r < Od:
There is no visible splitting of energy levels but there develops a tendency
for the splitting of energy levels.
(iii) r = Oc:
The interaction between the outermost shell electrons of neighbouring
silicon atoms becomes appreciable and the splitting of the energy levels
commences.

(iv) Ob < r < Oc:

The energy corresponding to the s and p levels of each atom gets slightly
changed. Corresponding to a single s level of an isolated atom, we get 2N
levels. Similarly, there are 6N levels for a single p level of an isolated atom.
Since N is a very large number (≈ 1029 atoms / m3) and the energy of each level
is of a few eV, therefore, the levels due to the spreading are very closely
spaced. The spacing is ≈ 10-23 eV for a 1 cm3 crystal.

The collection of very closely spaced energy levels is called an energy band.

(v) r = Ob:
The energy gap disappears completely. 8N levels are distributed
continuously. We can only say that 4N levels are filled and 4N levels are
empty.
(v) r = Oa:
The band of 4N filled energy levels is separated from the band of 4N unfilled
energy levels by an energy gap called forbidden gap or energy gap or
band gap.
The lower completely filled band (with valence electrons) is called the
valence band and the upper unfilled band is called the conduction band.
Note:
1. The exact energy band picture depends on the relative orientation of
atoms in a crystal.
2. If the bands in a solid are completely filled, the electrons are not permitted
to move about, because there are no vacant energy levels available.
Metals:
The first possible energy band diagram
shows that the conduction band is only
partially filled with electrons. • • • • • •
Partially filled
With a little extra energy the electrons Conduction Band
can easily reach the empty energy
levels above the filled ones and the
conduction is possible. Conduction Band

The second possible energy band

diagram shows that the conduction
band is overlapping with the valence
band.
This is because the lowest levels in the
conduction band needs less energy
than the highest levels in the valence
band.
The electrons in valence band overflow
into conduction band and are free to
move about in the crystal for
conduction.
• • • • • •
Valence Band
The highest energy level in the
conduction band occupied by
electrons in a crystal, at absolute 0
temperature, is called Fermi Level.
The energy corresponding to this
energy level is called Fermi energy.
If the electrons get enough energy
to go beyond this level, then
conduction takes place.
Semiconductors:
At absolute zero temperature, no
electron has energy to jump from Conduction Band
valence band to conduction band
and hence the crystal is an insulator.
Forbidden Energy Gap ≈1 eV
At room temperature, some valence ••• •• •
electrons gain energy more than the Valence Band
energy gap and move to conduction
band to conduct even under the
influence of a weak electric field. Eg-Si = 1.1 eV EgGe= 0.74 eV

Eg
- Since Eg is small, therefore, the fraction
The fraction is pαe kB T
is sizeable for semiconductors.

As an electron leaves the valence band, it leaves some energy level in band
as unfilled.
Such unfilled regions are termed as ‘holes’ in the valence band. They are
mathematically taken as positive charge carriers.
Any movement of this region is referred to a positive hole moving from one
position to another.
Insulators:
Electrons, however heated, can not Conduction Band
practically jump to conduction band
from valence band due to a large
energy gap. Therefore, conduction is Forbidden Energy Gap ≈6 eV
not possible in insulators.
Eg-Diamond = 7 eV
•Valence
• • • •Band
•
Electrons and Holes:
On receiving an additional energy, one of the electrons from a covalent band
breaks and is free to move in the crystal lattice.
While coming out of the covalent bond, it leaves behind a vacancy named
‘hole’.
An electron from the neighbouring atom can break away and can come to the
place of the missing electron (or hole) completing the covalent bond and
creating a hole at another place.
The holes move randomly in a crystal lattice.
The completion of a bond may not be necessarily due to an electron from a
bond of a neighbouring atom. The bond may be completed by a conduction
band electron. i.e., free electron and this is referred to as ‘electron – hole
recombination’.
Intrinsic or Pure Semiconductor:
Valence electrons
Covalent Bond
Ge Ge Ge Ge
Broken Covalent Bond

Free electron ( - )
Ge Ge Ge Ge Hole ( + )

Ge Ge Ge Ge C.B
+

Eg 0.74 eV
Ge Ge Ge Ge V.B
+ +

Heat Energy
Intrinsic Semiconductor is a pure semiconductor.
The energy gap in Si is 1.1 eV and in Ge is 0.74 eV.
Si: 1s2, 2s2, 2p6,3s2, 3p2. (Atomic No. is 14)
Ge: 1s2, 2s2, 2p6,3s2, 3p6, 3d10, 4s2, 4p2. (Atomic No. is 32)
In intrinsic semiconductor, the number of thermally generated electrons
always equals the number of holes.
So, if ni and pi are the concentration of electrons and holes respectively, then
n i = p i.
The quantity ni or pi is referred to as the ‘intrinsic carrier concentration’.

Doping a Semiconductor:
Doping is the process of deliberate addition of a very small amount of
impurity into an intrinsic semiconductor.
The impurity atoms are called ‘dopants’.
The semiconductor containing impurity is known as ‘impure or extrinsic
semiconductor’.
Methods of doping:
i) Heating the crystal in the presence of dopant atoms.
ii) Adding impurity atoms in the molten state of semiconductor.
iii) Bombarding semiconductor by ions of impurity atoms.
Extrinsic or Impure Semiconductor:
N - Type Semiconductors:

Ge Ge Ge
C.B

- 0.045 eV
Eg = 0.74 eV
Ge As Ge
+ V.B

Ge Ge Ge Donor level
+

When a semiconductor of Group IV (tetra valent) such as Si or Ge is doped

with a penta valent impurity (Group V elements such as P, As or Sb), N –
type semiconductor is formed.
When germanium (Ge) is doped with arsenic (As), the four valence
electrons of As form covalent bonds with four Ge atoms and the fifth
electron of As atom is loosely bound.
The energy required to detach the fifth loosely bound electron is only of
the order of 0.045 eV for germanium.
A small amount of energy provided due to thermal agitation is sufficient to
detach this electron and it is ready to conduct current.
The force of attraction between this mobile electron and the positively
charged (+ 5) impurity ion is weakened by the dielectric constant of the
medium.
So, such electrons from impurity atoms will have energies slightly less
than the energies of the electrons in the conduction band.
Therefore, the energy state corresponding to the fifth electron is in the
forbidden gap and slightly below the lower level of the conduction band.

This energy level is called ‘donor level’.

The impurity atom is called ‘donor’.
N – type semiconductor is called ‘donor – type semiconductor’.
Carrier Concentration in N - Type Semiconductors:
When intrinsic semiconductor is doped with donor impurities, not only does
the number of electrons increase, but also the number of holes decreases
below that which would be available in the intrinsic semiconductor.
The number of holes decreases because the larger number of electrons
present causes the rate of recombination of electrons with holes to increase.
Consequently, in an N-type semiconductor, free electrons are the majority
charge carriers and holes are the minority charge carriers.
If n and p represent the electron and hole concentrations respectively in
N-type semiconductor, then
n p = n i p i = ni 2

where ni and pi are the intrinsic carrier concentrations.

The rate of recombination of electrons and holes is proportional to n and p.
Or, the rate of recombination is proportional to the product np. Since the
rate of recombination is fixed at a given temperature, therefore, the product
np must be a constant.
When the concentration of electrons is increased above the intrinsic value
by the addition of donor impurities, the concentration of holes falls below
its intrinsic value, making the product np a constant, equal to ni2.
 P - Type Semiconductors:

Ge Ge Ge
C.B

Ge In Ge
Eg = 0.74 eV
0.05 eV
+
V.B

Ge Ge Ge Acceptor level
+

When a semiconductor of Group IV (tetra valent) such as Si or Ge is doped

with a tri valent impurity (Group III elements such as In, B or Ga), P – type
semiconductor is formed.
When germanium (Ge) is doped with indium (In), the three valence
electrons of In form three covalent bonds with three Ge atoms. The
vacancy that exists with the fourth covalent bond with fourth Ge atom
constitutes a hole.
The hole which is deliberately created may be filled with an electron from
neighbouring atom, creating a hole in that position from where the electron
jumped.
Therefore, the tri valent impurity atom is called ‘acceptor’.
Since the hole is associated with a positive charge moving from one position
to another, therefore, this type of semiconductor is called
P – type semiconductor.
The acceptor impurity produces an energy level just above the valence band.
This energy level is called ‘acceptor level’.
The energy difference between the acceptor energy level and the top of the
valence band is much smaller than the band gap.
Electrons from the valence band can, therefore, easily move into the acceptor
level by being thermally agitated.
P – type semiconductor is called ‘acceptor – type semiconductor’.
In a P – type semiconductor, holes are the majority charge carriers and the
electrons are the minority charge carriers.
It can be shown that, n p = n i p i = ni 2
Distinction between Intrinsic and Extrinsic Semiconductor:

S. No. Intrinsic SC Extrinsic SC

1 Pure Group IV elements. Group III or Group V elements
are introduced in Group IV
elements.

2 Conductivity is only slight. Conductivity is greatly

increased.

3 Conductivity increases with rise Conductivity depends on the

in temperature. amount of impurity added.

4 The number of holes is always In N-type, the no. of electrons is

equal to the number of free greater than that of the holes
electrons. and in P-type, the no. holes is
greater than that of the
electrons.
 Distinction between Semiconductor and Metal:

S. No. Semiconductor Metal

1 Semiconductor behaves like an
insulator at 0 K. Its conductivity
increases with rise in
temperature.
2 Conductivity increases with rise
in potential difference applied.
3 Does not obey Ohm’s law or
only partially obeys.
Conductivity decreases with
rise in temperature.
Conductivity is an intrinsic
property of a metal and is
independent of applied potential
difference.
Obeys Ohm’s law.

4 Doping the semiconductors with Making alloy with another metal

impurities vastly increases the decreases the conductivity.
conductivity.
Electrical Conductivity of Semiconductors:
I = I e + Ih Ih Ie

Ie = neeAve Ih = nheAvh
So, I = neeAve + nheAvh
If the applied electric field is small, I
then semiconductor obeys Ohm’s law.
V
= neeAve + nheAvh E
R E V
= eA (neve + nhvh) = e (neve + nhvh) since E =
ρ l
VA Mobility (μ) is defined as the drift
Or = eA (neve + nhvh) velocity per unit electric field.
ρl ρl
since R = 1
A = e (neμe + nhμh)
ρ
Note:
Or σ = e (neμe + nhμh)
1. The electron mobility is higher than the hole mobility.
2. The resistivity / conductivity depends not only on the
electron and hole densities but also on their mobilities.
3. The mobility depends relatively weakly on temperature. End of S & SC - I